Preparing viscose rayon



i d ates I 2,929,730 PREPARING VISCGS E RAYON Marion R. Lyt'ton, West Chester, Pa., asstg'nor' to Anterican Viscose Corporation, Philadelphia, P36, :2. corporafion of Delaware I No Drawing. Application December 5 i955 SerialNo. 550,856

4 Qlaims. c1. 106 165) solution and after shredding the treated cellulose mate-- 'rial, it is allowed to age.

The aged alkali cellulose'is then converted to a Xanthate by treatment with carbon disulfide. The cellulose tanthate is subsequently dissolved iii a causticsoda solution in an amount alcllltitd to provide a viscose of the desired cellulose and alkali content. After filtration, the viscose solution is allowed to ripen and is subsequently eiittrude'd through a shaped orifice into a suitable coagulating and regenerating. bath.

Injthe product-ion of shaped bodies such as filaments,

a coagulating and regenerating bath consisting of an "aqueous acid solution containing zinc sulfate. The filament may subsequently be passed through a hot aqueous bath where it is stretched to improve its properties such as tensile strength. The filament may then be passed through a dilute aqueous solution of sulfuric acid and sodium sulfate to complete the regeneration of the cellulose, in case it is not completely regenerated upon leaving the stretching stage. The filament is subsequently subjected to washing, purification, bleaching, possibly other treating operations and drying, being collectedeither before or after these treatments.

The filaments as formed by the conventional methods, consist of a'skin 'or outer shell portion and a core portion with a sharp line ot'deniarkation between the two.v The cross-section of the filaments exhibits a very irregular or crenulated exterior surface when even small amounts of Zinc Stilts 01 certain Ollie 1" p'olyvalent metal salts are present in the s inning bath. The skin and core portions of the filament represent differences in structure and these different portions possess different swelling and staining characteristics, the latter permitting a ready identification of skin and core.' The sharply irregular and crenulated surface structure has a relatively low abrasion r sistance and readily icks up foreign particles such as dirt. Although the core portion possesses a relatively high tensile strength, it has a low abrasion resistance and a low flexlife, is subject to fibrillation and is relatively stilt.

it has now been discovered that the presence of mall amounts of certain alkali-soluble alkylene oxide adduc'ts of o-dimethylarn'ino'meth yl' phenol: in viscose results in "the'viscose -solution is extruded through a spinner'et into a. 2,929,730 Patented Mai-.22, 1960 This invention contemplates the use of such compounds as are more technically classedas polyoiiyallcylene glycol ethers of o-dimethylan'iinornethyl phenol; for example, the others of ethylene, propylene and butylene glycols having from about 3 to about 100 or more alkylene oxide units per molecule, preferably between about 5 and 49 alkylene oxide units per molecule of odimethylaminomethyl phenol. It is obvious that for all practical purposes considering cost, ease of preparation, commercial availability and solubility in water and in alkali solutions, the ethylene oXide adducts or polyoxyethylene glycol ethe'r's are preferred. For purposes of illustration only, the invention is described by reference to the ethylene oxide adducts but it is to be understood that other alliylene oxide dducts such as propylene oxide adducts are equally satisfactory so long as they possess the re- .quired solubility. The productionof all skin products requires that certain minimum a'ndlimited amounts of the ether be in solution in the viscose. The ether may be conveniently added to the viscose in the form of a tion of products consisting entirely of skin and greater amounts alfect adversely the physical properties of the 1 products. Amounts within the preferred range are most effective in enhancing. the'chara'ct'eristics and properties of the products. The ether or adduct may be added at any desired stage in the production of the viscose such as in the preparation ,of the refinedwood pulpfor the ,manufacture of viscose, before or. during the shredding of the alkali cellulose, to the-xanthated cellulose while it is being dissolved in the caustic solution or to the viscose solution before or' after filtration. The adduct is preferably added after the cellulose xanthate has been dissolvedin the caustic solution and prior to filtration.

The viscosemay contain fromabout 4% to about 8% cellulose, the particular source of the cellulose being selected for the ultir'nate use of the regenerated cellulose product. The caustic soda contentma'y be from about 4% to'about 8% and the carbon disulfide. content may be from about 307 to about 50% based upon the weight of the cellulose. The modified viscose, that is, a viscose containing the small amount ofanalk'ylene oxide 'adduct of o dimethylaminomethyl phenol may have a salt test above about 8 and preferably above about 9 atthe time of spinning or extrusion. I

In order to obtain the' hnprovements enumerated hereinbefore, it is essential that the composition of the spinning bath be maintained within a well defined range. The presence of the ether or adduct in the viscose combined with these limited spinning baths results in the production of yarns of improved properties such as high tenacity, high abrasion resistance, high fatigue resistance and consis'ting' of filaments composed entirely of skin.

' Generically and in terms of the industrial art, the spinning b'ath is a low acid-high zinc spinning bath containing from about-10% to about' 25%' sodium sulfate and from about. 3% to about 15% zinc sulfate, preferably from 1 5% to 22%- sodium sulfate and from 4% to 9% zinc sulfate; Other metal sulfates such as iron, mam g'anese, nickel and the" like may be present and may re place some -of the zinc sulfate. The temperature of the spinning bath may vary from about 25 C. to about C., preferably between about 45 C. and about 70 Q. In the production of the all skin type filaments, the

temperature of the spinning bath isnot critical, however,

. and core.

ing skin and core.

vary directly with the temperature of the spinning bath. Thus, in the production of filaments for tire cord purposes in accordance with the method of this invention, the spinning bath is preferably maintained at a temperature between about 55 C. and 65" C. so as to obtain the desired high tensile strength.

The acid content of the spinning bath is balanced against the composition of the viscose. of the acid concentration, as is well known in the art, is just above the slubbing point, that is,the concentration at which small slubs of uncoagulated viscose appear in the strand as it leaves the spinning bath. For commercial operations, the acid concentration of the spinning The lower limit bath is generally maintained about 0.4% to 0.5% above I the slubbing point. For any specific'viscose composition, the acid concentration of the spinning bath must be maintained above the slubbing point and below the point at which the neutralization of the caustic of the viscose is sufiiciently rapid to form a filament having a skin and core.

There is a maximum acid concentration for any specific viscose composition beyond which the neutralization is sufficiently rapid to produce filaments having a skin For example, in general, the acid concentration of the spinning baths which are satisfactory for the production of the all skin products from a 7% cellulose, 6% caustic-viscoseand containing the alkylene oxide adducts lies between about 5% and about 7.5% to 7.8%. The acid concentration may be increased as the amount of the derivative is increased and also as the salt test of the viscose is increased. There is an upper limit, however, for the acid concentration based upon the amount of adduct and the concentration of caustic in the viscose. All skin products cannot be obtained if the acid concentration is increased above the maximum value although the amount of the ether is increased beyond about 3% while other conditions are maintained constant.

' Increasing the caustic soda content of the viscose beyond about 8% is uneconomical for commercial production methods. For example, a viscose containing about 7% cellulose, about 6% caustic soda, about 36% (based on the weight of cellulose) carbon disulfide, and 1% (based on the Weight of cellulose) of an ethylene oxide adduct of o-dimethylaminomethyl phenol containing about ethylene oxide units per molecule, and having a salt test of about 9.5 when extruded into spinning baths containing 16 to 20% sodium sulfate, 4 to 8% zinc sulfate and sulfuric acid not more than about 7.75% results 1 in the production of all skin filaments. Lesser amounts of sulfuric acid may be employed. Greater amounts of sulfuric acid result in the production of products hav- A lowering of the amount of the ether, the lowering of the caustic soda content or the lowering of the salt test of the viscose reduces the maximum permissible acid concentration for the production of all skin filaments. It has been determined that the maximum concentration of acid which is permissible for the production of all skin products is about 8.5%.

The presence of the ethers or adducts in the viscose retards the coagulation and, therefore, the amount of adduct employed must be reduced at high spinning speeds. Thus, for-optimum physical characteristics of an all skin yarn'formed from a viscose as above and at a spinning speed'of about 50 meters per minute, the adduct is .employed .in amounts within the lower portion of the range, for example, about 1%. The determination of the specific maximum and optimum concentration of acid for any specific viscose, spinning bath and spinning speed is a matter of simple experimentation for those skilled in the art. The extruded viscose must, of course, be immersed or maintained in the spinning bath for a period sufiicient to effect relatively complete coagulation of the viscose, that is, the coagulation must be sufiicient'so that the filaments will not adhere to each other as they are bro gh together and withdrawn from the bath.

In the production of filaments for such purposes as the fabrication of tire cord, the filaments are preferably stretched after removal from the initial coagulating and regenerating bath. From the initial spinning bath, the filaments may be passed through a hot aqueous bath which may consist of hot water or a dilute acid solution and may be stretched from about 70% to about 120%, preferably between 75% and 100%. Yarns for other textile purposes may be stretched as low as 20%. The precise amount of stretching will be dependent upon the desired tenacity and other properties and the specific type of product being produced. If desired, the filaments may be stretched in air. It is to be understood that the 1nvention is notrestricted tothe production of filaments and yarns but it is also applicable to other shaped bodies such as sheets, films, tubes and the like. The filaments may then be passed through a final regenerating bath which may contain from about 1% to about 5% sulfuric acid and from about 1% to about 5% sodium sulfate with or without small amounts of zinc sulfate if regeneration has not previously been completed.

The treatment following the final regenerating bath, or the stretching operation where regeneration has been completed, may consist of a washing step, a desulfurizing step, the application of a finishing or plasticizing material and drying before or after collecting, or may include other desired and conventional steps such as bleaching and the like. The treatment after regeneration will be dictated by the specific type of shaped body and the proposed use thereof.

Regenerated cellulose filaments prepared from viscose containing the small amounts of the alkylene oxide adducts or polyoxyalkylene glycol ethers and spun in the spinning baths of limited acid content have a smooth or non-crenulated surface and consist substantially entirely of skin. Because of the uniformity of structure throughout the filament, the swelling and staining characteristics are uniform throughout the cross-section of the filament. Filaments produced pursuant to this invention and consisting entirely of skin have a high toughness and .a greater flexing life than filaments as produced according to prior methods which may be attributed by the uniformity in skin structure throughout the filament Although the twisting of conventional filaments, as m the production of tire cord, results in an appreciable loss of tensile strength, there is appreciably less loss in tenslle strength in the production of twisted cords from the filaments consisting entirely of skin. Filaments prepared from viscose containing the alkylene oxide adducts have a high tensile strength as compared to normal regenerated cellulose filaments, have superior abrasion and fatigue resistance characteristics and have a high flex-life. Such filaments are highly satisfactory for the production of cords for the reinforcement of rubber products such as pneumatic tire casings, but the filaments are not restricted to such uses and may be used for other textile applications.

The invention may be illustrated by reference to the preparation of regenerated cellulose filaments from a viscose containing about 7.4% cellulose, about 6.6%

caustic soda, and having a total carbon disulfide content of about 36% based on the weight of the cellulose. The

on the weight of the cellulose and churning for about 2 4: ;,hours. The cellulose xanthate was then dissolved in caustic soda solution. The desired amount of the ethylene oxide adduct of o-dimethylaminomethyl phenol was added to the solution and mixed for about /fi hour. The

'viscose was then allowed to ripen for about 28 hours at 18 C.

Example 1 4 Approximately 1% (based on the weight of the cellumolecule, was added to and incorporated in the viscose as described above. The viscose employed in the spinning of filaments had a salt test of 10.4. The viscose was extruded through a spinneret to form 203 denier, 100 filament yarn at a rate of about 22- meters per minute. The coagulating and regenerating bath was maintained at a temperature of about 60 C. and contained 7.8% sulfuric acid, 5% zinc sulfate and 17% sodium sulfate. The yarn was stretched about 82% While passing through a hot water bath at 95 C. The yarn was collected in a spinning box, washed free of acids and salts and dried.

The individual filaments have a smooth, non-crenulated exterior surface and consist entirely of skin, no core being detectable at high magnification (e.g. 1500 The filaments of a control yarn spun with the same viscose but without the addition of the modified agent and spun under the same conditions, exhibit a very irregular and serrated surface and are composed of about 65% skin and the balance core with a sharp line ofdernarkation between the skin and core. Other physical properties are set forth in'the table which follows the examples.

Example 2 To a viscose as described above, there was added 1% of the same ethylene oxide adduct. The viscose had a salt test of 10.8 and was spun into a 200 denier, 100 filament yarn by extrusion into a spinning bath containing 8.2% sulfuric acid, 5% zinc sulfate and 16% sodium sulfate. The bath was maintained at 60 C. and the extrusion rate was about 43 meters per minute. The filaments were stretched about 74%, collected in a spinning box, washed free of acids. and salts and dried.

The individual filaments were readily distinguishable from control filaments in that they have a smooth, noncrenulated surface and consist entirely of skin while the control filaments have a very irregular and serrated surface and consist of about 65% skin and the balance core with a sharp line of demarkation between the skin and core. Other physical properties are set forth in the table which follows:

Although the tenacity and elongation are the only properties set forth, they have. been chosen because of the ease and simplicity with which such properties may be determined. In some instances, products made in accordance with this invention do not exhibit improvements in tenacity and elongation, however, the products consist of a smooth-surfaced, all skin structure and possess improved abrasion resistance, flex-life and other properties as disclosed hereinbefore.

One of the properties of viscose rayon which has limited its uses is its relatively high cross-sectional swelling when wet with water, this swelling amounting to from about 65% to about 80% for rayon produced by con-' ventional methods. Rayon filaments produced in accordance with the method of this invention have an appreciably lower cross-sectional swelling characteristic, the swelling amounting to from about 45% to about 60%.

If desired, small amounts of the ether may be added to the spinning bath. Since the ethers are water-soluble, some of the ether will be leached from the filament or other shaped body and will be present in the bath.

The alkylene oxide ethers may be added to any desired viscose such as those normally used in industry, the specific viscose composition set forth above, being merely for illustrative purposes. The ethers may be added at any desired stage in the production of the viscoseand may be present in the cellulosic raw material although it may be necessary to adjust the amount present to produce a viscose having the proper proportions of the adduct at the time of spinning.

The term skin is employed to designate that portion of regenerated cellulose filaments which is permanently stained or dyed by the following procedure. A microtorne section of one or more of the filaments mounted in a Wax block is taken and mounted on a slide with Meycrs albumin fixative. After dewaxing in xylene, the section is placed in successive baths of and 30% alcohol for a few moments each, and it is then stained in 2% aqueous solution of Victoria Blue BS conc. (General Dyestuffs Corp.) for 1 to 2 hours. At this point, the entire section is blue. By rinsing the section first in distilled water and then in one or more baths composed of 10% Water and 90% dioxane for a period varying from 5 to 3.0 minutes depending on the particular filaments, the dye is entirely removed from the core, leaving it restricted to the skin areas.

While preferred embodiments of the invention have been disclosed, the description is intended to be illustrative and it is to be understood that changes and variations may be made without departing from the spirit and scope of the inventionas defined by the appended claims.

I claim: a

1. A viscose spinning solution containing a small amount of an alkali-soluble polyoxyalkylene glycol ether of o-dimethylaminomethyl phenol, the polyoxyalkyleneglycol radical in the ether being selected from the group consisting of polyoxyethylene glycol radicals, polyoxypropylene glycol radicals and polyoxybutylene glycol radicals, the ether containing from about 3 to about 100 alkylene oxide units per molecule, said small amount of v the ether being a quantity sufiicient to impart a smooth, non-crenulated surface and a substantially all skin struc ture to products formed by spinning the viscose at a salt test of at least 8 into an aqueous bath containing from 10% to 25% sodium sulfate, from 3% to 15% zinc sulfate and sulfuric acid in a percentage not exceeding 8.5%, but the quantity beinginsufficient to adversely alfect the physical properties of such products. a

2. A viscose spinning solution as defined in claim 1 wherein the ether is a polyoxyalkylene glycol ether of o-dimethylaminomethyl phenol.

3. A viscose spinning solution containing from about 4% to about 8% cellulose and from about 1% toabout 3%, based on theweight of the cellulose in the viscose, of an alkali-soluble polyoxyalkylene glycol ether of o-dimethylaminomethyl phenol, the polyoxyalkylene glycol radical in the ether being selected from the group consisting of polyoxyethylene glycolv radicals, polyoxypro- I pylene glycol radicals and polyoxybutylene glycol radicals, the ether containing from about 3 to about alkylene oxide units per molecule. I 1

4. A viscose spinning solution as defined in claim 3 wherein the ether is a polyoxyethylene glycol ether of o-dimethylaminomethyl phenol.

References Cited-in the file of this patent UNITED STATES PATENTS Great Britain Dec. 14, 1955 

1. A VISCOSE SPINNING SOLUTION CONTAINING A SMALL AMOUNT OF ALKALI-SOLUBLE POLYOXALKYLENE GLYCOL ETHER OF O-DIMETHYLAMINOMETHYL PHENOL, THE POLYOXYALKYLENE GLYCOL RADICAL IN THE ETHER BEING SELECTED FROM THE GROUP CONSISTING OF POLYOXETHYLENE GLYCOL RADICALS, POLYOXYPROPYLENE GLYCOL RADICALS AND POLYOXYBUTYLENE GLYCOL RADICALS, THE ETHER CONTAINING FROM ABOUT 3 TO ABOUT 100 ALYLENE OXIDE UNITS PER MOLECULE, SAID SMALL AMOUNT OF THE ETHER BEING A QUANTITY SUFFICIENT TO IMPART A SMOOTH, NON-CRENULATED SURFACE AND A SUBSTANTIALLY ALL SKIN STRUCTURE TO PRODUCTS FORMED BY SPINNING THE VISCOSE AT A SALT TEST OF AT LEAST 8 INTO AN AQUEOUS BATH CONTAINING FROM 10% TO 25% SODIUM SULFATE, FROM 3% TO 15% ZINC SULFATE AND SULFURIC ACID IN A PERCENTAGE NOT EXCEEDING 8.5%, BUT THE QUANTITY BEING INSUFFICIENT TO ADVERSELY AFFECT THE PHYSICAL PROPERTIES OF SUCH PRODUCTS. 